Needle trap device technique: From fabrication to sampling.

Needle Trap Device (NTD) as a novel, versatile, and eco-friendly technique has played an important role in analytical and environmental chemistry. The distinctive role of this interdisciplinary technique can be defended through the sampling and analysis of biological samples and industrial pollutants in gaseous and liquid environments. In recent years, significant efforts have been made to enhance the performance of the needle trap device resulting in the development of novel extraction routes by various packing materials with improved selectivity and enhanced adsorption characteristics. These achievements can lead to the facilitated pre-concentration of desired analytes. This review tries to have a comparative and comprehensive survey of the three important areas of NTD technique: I) Fabrication and preparation procedures of NTDs; II) Sampling techniques of pollutants using NTDs; and III) Employed materials as adsorbents in NTDs. In the packing-material section, the commercial and synthetic adsorbents such as carbon materials, metal-organic frameworks, aerogel, and polymers are considered. Furthermore, the limitations and potential areas for future development of the NTD technique are presented.

Investigation of microbial fuel cell performance based on the nickel thin film modified electrodes.

Microbial fuel cells (MFCs) are a self-sustaining and environmentally friendly system for the simultaneous was tewater treatment and bioelectricity generation. The type and material of the electrode are critical factors that can influence the efficiency of this treatment process. In this study, graphite plates and carbon felt were modified through the electrodeposition of nickel followed by the formation of a biofilm, resulting in conductive bio-anode thin film electrodes with enhanced power generation capacity. The structural and morphological properties of the electrode surfaces were characterized using X-ray diffraction, energy-dispersive X-ray spectroscopy, elemental mapping, and field-emission scanning electron microscopy techniques. Maximum voltage, current density, and power generation were investigated using a dual-chamber MFC equipped with a Nafion 117 membrane and bio-nickel-doped carbon felt (bio-Ni@CF) and bio-nickel-doped graphite plate (bio-Ni@GP) electrodes under constant temperature conditions. The polarization and power curves obtained using different anode electrodes revealed that the maximum voltage, power and current density achieved with the bio-Ni@CF electrode were 468.0 mV, 130.72 mW/m2 and 760.0 mA/m2 respectively. Moreover, the modified electrodes demonstrated appropriate stability and resistance during successful runs. These results suggest that nickel-doped carbon-based electrodes can serve as suitable and stable supported catalysts and conductors for improving efficiency and increasing power generation in MFCs.

Investigation of organophosphorus (OPs) compounds by a needle trap device based on mesoporous organo-layered double hydroxide (organo-LDH).

Organophosphorus (OPs) compounds can endanger human health and the environment by inhibiting the acetylcholinesterase enzyme. But these compounds have been widely used as pesticides due to their effectiveness against all kinds of pests. In this study, a Needle Trap Device (NTD) packed with mesoporous organo-layered double hydroxide (organo-LDH) material and coupled with gas chromatography-mass spectrometry (GC-MS) was employed for the sampling and analysis of OPs compounds (diazinon, ethion, malathion, parathion, and fenitrothion). In this way, the [magnesium-zinc-aluminum] layered double hydroxide ([Mg-Zn-Al] LDH) modified with sodium dodecyl sulfate (SDS) as a surfactant was prepared and characterized by FT-IR, XRD, BET, and FE-SEM, EDS, and elemental mapping techniques. Then, various parameters such as relative humidity, sampling temperature, desorption time, and desorption temperature were evaluated by the mesoporous organo-LDH:NTD method. The optimal values of these parameters were determined using response surface methodology (RMS) and central composite design (CCD). The optimal temperature and relative humidity values were obtained as 20 °C and 25.0%, respectively. On the other hand, the desorption temperature and time values were in the range of 245.0-254.0 °C and 5 min, respectively. The limit of detection (LOD) and limit of quantification (LOQ) were reported in the range of 0.02-0.05 mg m-3 and 0.09-0.18 mg m-3, respectively, which shows the high sensitivity of the proposed method compared to the usual methods. The repeatability and reproducibility of the proposed method (by calculating the relative standard deviation) was estimated in the range of 3.8-10.10 which indicates the acceptable precision of the organo-LDH:NTD method. Also, the desorption rate of the stored needles at 25 °C and 4 °C, was determined to be 86.0% and 96.0%, respectively after 6 days. The results of this study proved that the mesoporous organo-LDH:NTD method can be utilized as a fast, simple, environmentally friendly, and effective method for sampling and determining OPs compounds in the air.

Urinary bio-monitoring of aromatic amine derivatives by new needle trap device packed with the multi-component adsorbent.

Aromatic amines are a large group of chemical compounds that have attracted the attention of researchers due to their toxicity and carcinogenicity. This study aimed to develop an efficient method for sampling and analysis of aromatic amines (Aniline, N, N-dimethylaniline, 2-chloroaniline, and 3-chloroaniline) from the vapour phase (headspace) of urine samples. For the implementation of this plan, a needle trap device packed with the three-component adsorbent consisting of nano-Hydroxy Apatite (nHA), Zeolite (Ze), and Metal-Organic Framework (MOF) equipped with GC-FID was employed for the first phase. Examination of the prepared adsorbents was performed by FT-IR, PXRD, and FE-SEM techniques. The optimal value of considerable parameters such as time and temperature of extraction, salt content, and pH were established using the Response Surface Methodology-Central Composite Design (RMS-CCD) method. In this way, the optimal extraction of targeted analytes was accomplished in 41 min at 41 °C with NaCl content of 33.0% (w/v) and pH: 13.0, respectively. Also, the repeatability and reproducibility of the method were calculated to be in the range of 2.2-7.1% and 3.9-8.1%, respectively, which indicates the acceptable precision of the method. Also, the limit of detection (LOD) and limit of quantification (LOQ) were determined in the range of 0.3-32.0 ng.L-1 and 0.8-350.0 ng.L-1, respectively, which proves the high sensitivity of the proposed method. Furthermore, the recovery percent of the extracted analytes was concluded in the range of 97.0-99.0% after 6 and 30 days of the sampling and storage at 25 °C and 4 °C, respectively. Finally, the designed procedure was employed in the analysis of the above-mentioned aromatic amines in the real urine samples. The achieved results illustrate that the three-component absorbent system (nHA;Ze;MOF@NTD) can be introduced as an efficient, fast-response, sensitive, and versatile procedure for trace analysis of the different aromatic amine compounds in public and occupational health.

Kinetic studies of dexamethasone degradation in aqueous solution via a photocatalytic UV/H2O2/MgO process.

Wastewaters discharged from different industries and hospitals may contain pharmaceuticals, especially dexamethasone (DEX). Thus, we applied the UV/H2O2 photocatalytic method in the presence of the MgO nanoparticles to remove dexamethasone from synthetic wastewater. Moreover, the effects of parameters such as pH (3-11), hydrogen peroxide concentration (1-8 mM), initial DEX concentration (5-30 mg/L), and catalyst dosage (0.01-0.2 g/L) during the reaction times (0-30 min) were investigated. Furthermore, the efficiency of UV/H2O2 in the presence and absence of catalysts was investigated. The photocatalyst is characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), and Fourier-transform infrared spectroscopy (FTIR) techniques. It was found that the removal rate was enhanced by decreasing pH and the initial dexamethasone concentration. The removal rate was enhanced somewhat with concentrations of hydrogen peroxide and MgO. In the case of UV/H2O2/MgO, 87% removal efficiency was achieved, under the optimal conditions: pH 3, contact time of 30 min, dexamethasone concentration of 20 mg/L, H2O2 of 0.5 mM, and UV radiation of 55 watts. The kinetic data indicated that the reaction followed the second-order kinetic model. The results showed that the UV/H2O2 photochemical process can efficiently remove dexamethasone from aqueous in the presence of a MgO catalyst, and the mineralization efficiency was reached at about 98%.

Application of MIL-53(Al)-NH2 as a Dispersive Microsolid-Phase Extraction Material for Determination of Cyclophosphamide in Urine by High-Performance Liquid Chromatography.

In this paper, an aluminum-based metal-organic framework (MIL-53(Al)-NH2) was synthesized and employed as a well-known and efficient dispersive microsolid-phase extraction (Dµ-SPE) sorbent for reliable determination of cyclophosphamide in urine samples by the high-performance liquid chromatography (HPLC) technique. The synthesized MIL-53(Al)-NH2 was characterized by FT-IR, PXRD, FE-SEM, and EDS for more details. Then, the effective parameters of the preconcentration and extraction of urinary cyclophosphamide including the amount of the solid sorbent, the pH of the sample, sample volume, extraction and desorption time, and the type and volume of elution solvent were thoroughly investigated and optimized. According to the results, a linear dynamic range of 0.14-120 µg mL-1 with a good correlation coefficient (R 2 = 0.998) and a limit of detection (LOD) of 0.05 µg mL-1 were obtained with intra- and interday relative standard deviations (n = 9) of 3.13 and 3.99% in optimized conditions, respectively. Furthermore, the absolute recovery of urinary cyclophosphamide at three concentrations (0.5, 50.0, and 100.0 µg mL-1) was 94.0%. Finally, the optimal condition of the developed method was successfully applied to the extraction and analysis of cyclophosphamide from the real urine samples with satisfactory recovery (94.0-97.0%) and acceptable precision (<4.1%). The findings proved that MIL-53(Al)-NH2 can be utilized as a suitable adsorbent for highly reliable extraction of cyclophosphamide in biological matrices.

Urinary bio-monitoring of amphetamine derivatives by needle trap device packed with the zirconium-based metal-organic framework.

In this research, zirconium-based metal-organic framework was utilized as a novel and efficient porous adsorbent for headspace extraction of Amphetamine, Methamphetamine, and Fenfluramine from the urine samples by a needle trap device (NTD). The Zr-UiO-66-PDC was electrosynthesized at the green conditions and characterized by various analyses such as FT-IR, XRD, FE-SEM, EDS, and elemental mapping techniques. Then, the effective parameters on the NTD efficiency such as salt content, pH, extraction/desorption temperature and time were evaluated and optimized by response surface methodology. The optimal extraction of amphetamine compounds was accomplished in 50 min at 70 ºC at the situation with NaCl content of 27% and pH: 11.90. The limit of detection, and limit of quantification factors were determined to be 0.06-0.09 and 0.5-0.8 ng mL-1, respectively. Furthermore, the precision and accuracy (intra- and inter-day) of the employed procedure in the term of relative standard deviation (RSD) were calculated in the range of 8.0-9.0% and 6.8-9.8%, respectively. Also, the recovery percent of the extracted analytes were concluded in the range of 95.0-97.0% after 10 days from the sampling and storage at 4 °C. Finally, the proposed procedure was involved in the analysis of amphetamine compounds in the real urine samples. These results were proved the proposed Zr-UiO-66-PDC@HS-NTD technique coupled with GC-FID can be used as an eco-friendly, fast-response, sensitive, and efficient drug test procedure for trace analysis of the amphetamine compounds in urine samples.

Facile fabrication of amino-functionalized MIL-68(Al) metal-organic framework for effective adsorption of arsenate (As(V)).

An amino-functionalized MIL-68(Al) metal-organic framework (amino-MIL-68(Al) MOF) was synthesized by solvothermal method and then characterized by FESEM, XRD, FTIR, EDX-mapping, and BET-BJH techniques. In order to predict arsenate (As(V)) removal, a robust quadratic model (R2 > 0.99, F-value = 2389.17 and p value < 0.0001) was developed by the central composite design (CCD) method and then the genetic algorithm (GA) was utilized to optimize the system response and four independent variables. The results showed that As(V) adsorption on MOF was affected by solution pH, adsorbent dose, As(V) concentration and reaction time, respectively. Predicted and experimental As(V) removal efficiencies under optimal conditions were 99.45 and 99.87%, respectively. The fitting of experimental data showed that As(V) adsorption on MOF is well described by the nonlinear form of the Langmuir isotherm and pseudo-second-order kinetic. At optimum pH 3, the maximum As(V) adsorption capacity was 74.29 mg/g. Thermodynamic studies in the temperature range of 25 to 50 °C showed that As(V) adsorption is a spontaneous endothermic process. The reusability of MOF in ten adsorption/regeneration cycles was studied and the results showed high reusability of this adsorbent. The highest interventional effect in inhibiting As(V) adsorption was related to phosphate anion. The results of this study showed that amino-MIL-68(Al) can be used as an effective MOF with a high surface area (> 1000 m2/g) and high reusability for As(V)-contaminated water.

Application of a needle trap device packed with a MIP@MOF nano-composite for efficient sampling and determination of airborne diazinon pesticide.

In this research, a novel, selective, and efficient porous adsorbent nano-composite comprising a molecularly imprinted polymer and a metal-organic framework (MIP@MOF) was employed for sampling, extraction and analysis of diazinon from the air by a needle trap device (NTD), for the first time. The synthesized MIP@MOF sorbent was characterized by the FT-IR, XRD, FE-SEM, TEM, and EDS techniques. Then, the effective parameters of the sampling (temperature and humidity) and desorption (time and temperature) process were optimized by response surface methodology (RSM). The optimum values of temperature and humidity of the sampling chamber were estimated to be 20 °C and 25.0%, respectively. Also, the highest response during the analyte desorption was obtained at 262 °C and 4.5 minutes. For more details, the performance of the MIP@MOF:NTD method was evaluated by determination of important parameters such as repeatability, reproducibility, the limit of detection (LOD), and the limit of quantification (LOQ), and then compared with the NIOSH 5600 standard method. The values of LOD and LOQ for the targeted analyte were determined to be 0.02 and 0.1 µg m-3, respectively. Also, the repeatability and reproducibility of the proposed method were obtained in the range of (3.9-5.1)% and (5.1-6.4)%, respectively, which proved the acceptable precision of the method. Furthermore, the results of this study exhibited a high correlation coefficient (R 2 = 0.9781) between the proposed method and the recommended NIOSH method. Finally, the proposed procedure was utilized for sampling and determination of the airborne diazinon in real conditions. These results indicated that the proposed MIP@MOF:NTD method can be employed as a fast, simple, environmentally friendly, selective, and effective procedure for sampling and determining diazinon in air.

Effect of different concentrations of substrate in microbial fuel cells toward bioenergy recovery and simultaneous wastewater treatment.

Microbial fuel cells (MFCS) is a promising and expanding technology able to eliminate various pollutants of wastewater while converting its chemical energy into power energy using biocatalysts. The potential application of double-chamber microbial fuel cell (DC-MFC) for chemical oxygen demand (COD) removal and generated power from wastewater in the different conditions is investigated. DC-MFC is operated with anaerobic sludge as an active biocatalyst in an anode section, an aerobic cathode section and a Nafion117 membrane as a separator. The performance of the bioreactor is determined with different concentrations of chemical oxygen demand (COD) loadings in the MFC process, in terms of COD removal, power generation and columbic efficiencies. The results illustrated that COD removal efficiency increased at the high concentrations of organic matter. So that at COD concentration of 2000.0 mg/L the highest COD removal efficiency (84%) was obtained. But with increasing substrate initial concentration to 10000.0 mg/L the efficiency decreased to 79%. The important outputs of the system like the highest voltage, maximum generated power, current density, and energy efficiency with the 100,000 mg/L COD are 447 mV, 50.7 mW/m2, 570.0 mA/m2, and 18.6%, respectively. The optical density levels increased due to bacterial growth while pH severely decreased in the anode chamber when using high-concentration substrates in the MFC.

Anodic electrosynthesis of MIL-53(Al)-N(CH2PO3H2)2 as a mesoporous catalyst for synthesis of novel (N-methyl-pyrrol)-pyrazolo[3,4-b]pyridines via a cooperative vinylogous anomeric based oxidation.

In this paper, the MIL-53(Al)-NH2 metal-organic frameworks (MOFs) was prepared based on the anodic electrosynthesis under green conditions. The anodic electrosynthesis as an environmentally friendly procedure was performed in the aqueous solution, room temperature, atmospheric pressure, and in the short reaction time (30 min). Also, the employed procedure was accomplished without the need for the ex-situ salt and base/probase additives as cation source and ligand activating agent at the constant current mode (10.0 mA cm-2). The electrosynthesized MOFs was functionalized with phosphorus acid tags as a novel mesoporous catalyst. This mesoporous catalyst was successfully employed for synthesis of new series (N-methyl-pyrrol)-pyrazolo[3,4-b]pyridines by one-pot condensation reaction of 3-methyl-1-phenyl-1H-pyrazol-5-amine, 3-(1-methyl-1H-pyrrol-2-yl)-3-oxopropanenitrile and various aromatic aldehydes (mono, bis and tripodal). This catalyst proceeded the organic synthetic reaction via a cooperative vinylogous anomeric based oxidation mechanism with a marginal decreasing its catalytic activity after recycling and reusability.

Synthesis and application of [Zr-UiO-66-PDC-SO3H]Cl MOFs to the preparation of dicyanomethylene pyridines via chemical and electrochemical methods.

A metal-organic framework (MOF) with sulfonic acid tags as a novel mesoporous catalyst was synthesized. The precursor of Zr-UiO-66-PDC was synthesized both via chemical and electrochemical methods. Then, zirconium-based mesoporous metal-organic framework [Zr-UiO-66-PDC-SO3H]Cl was prepared by reaction of Zr-UiO-66-PDC and SO3HCl. The structure of [Zr-UiO-66-PDC-SO3H]Cl was confirmed by FT-IR, PXRD, FE-SEM, TEM, BET, EDX, and Mapping analysis. This mesoporous [Zr-UiO-66-PDC-SO3H]Cl was successfully applied for the synthesis of dicyanomethylene pyridine derivatives via condensation of various aldehyde, 2-aminoprop-1-ene-1,1,3-tricarbonitrile and malononitrile. At the electrochemical section, a green electrochemical method has successfully employed for rapid synthesis of the zirconium-based mesoporous metal-organic framework UiO-66-PDC at room temperature and atmospheric pressure. The synthesized UiO-66-PDC has a uniform cauliflower-like structure with a 13.5 nm mean pore diameter and 1081.6 m2 g-1 surface area. The described catalyst [Zr-UiO-66-PDC-SO3H]Cl was also employed for the convergent paired electrochemical synthesis of dihydropyridine derivatives as an environmentally friendly technique under constant current at 1.0 mA cm-2 in an undivided cell. The proposed method proceeds with moderate to good yields for the model via a cooperative vinylogous anomeric based oxidation.

Electrocatalytic degradation of diuron herbicide using three-dimensional carbon felt/ß-PbO2 anode as a highly porous electrode: Influencing factors and degradation mechanisms.

Traditional planar PbO2 anodes have been used extensively for the electrocatalytic degradation process. However, by using porous PbO2 anodes that have a three-dimensional architecture, the efficiency of the process can be significantly upgraded. In the current study, carbon felt (CF) with a highly porous structure and a conventional planar graphite sheet (G) were used as electrode substrate for PbO2 anodes. Both CF/ß-PbO2 and G/ß-PbO2 anodes were prepared by the anodic deposition method. The main properties of the electrodes were characterized by XRD, EDX-mapping, FESEM, and BET-BJH techniques. The electrocatalytic degradation of diuron using three-dimensional porous CF/ß-PbO2 anode was modeled and optimized by a rotatable central composite design. After optimizing the process, the ability of porous CF/ß-PbO2 and planar G/ß-PbO2 anodes to degrade and mineralize diuron was compared. The electrocatalytic degradation of the diuron was well described by a quadratic model (R2 > 0.99). Under optimal conditions, the kinetics of diuron removal using CF/ß-PbO2 anode was 3 times faster than the G/ß-PbO2 anode. The energy consumed for the complete mineralization of diuron using CF/ß-PbO2 anode was 2077 kWh kg-1 TOC. However, the G/ß-PbO2 anode removed only 65% of the TOC by consuming 54% more energy. The CF/ß-PbO2 had more stability (115 vs. 91 h), larger surface area (1.6287 vs. 0.8565 m2 g-1), and higher oxygen evolution potential (1.89 vs. 1.84 V) compared to the G/ß-PbO2. In the proposed pathways for diuron degradation, the aromatic ring and groups of carbonyl, dimethyl urea, and amide were the main targets for HO• radical attacks.

A novel bio-electro-Fenton system with dual application for the catalytic degradation of tetracycline antibiotic in wastewater and bioelectricity generation.

In this new insight, the potential application of the eco-friendly Bio-Electro-Fenton (BEF) system was surveyed with the aim of simultaneous degradation of tetracycline and in situ generation of renewable bioenergy without the need for an external electricity source. To shed light on this issue, catalytic degradation of tetracycline was directly accrued via in situ generated hydroxyl free radicals from Fenton's reaction in the cathode chamber. Simultaneously, the in situ electricity generation as renewable bioenergy was carried out through microbial activities. The effects of operating parameters, such as electrical circuit conditions (in the absence and presence of external resistor load), substrate concentration (1000, 2000, 5000, and 10 000 mg L-1), catholyte pH (3, 5, and 7), and FeSO4 concentration (2, 5, and 10 mg L-1) were investigated in detail. The obtained results indicated that the tetracycline degradation was up to 99.04 ± 0.91% after 24 h under the optimal conditions (short-circuit, pH 3, FeSO4 concentration of 5 mg L-1, and substrate concentration of 2000 mg L-1). Also, the maximum removal efficiency of anodic COD (85.71 ± 1.81%) was achieved by increasing the substrate concentration up to 2000 mg L-1. However, the removal efficiencies decreased to 78.29 ± 2.68% with increasing substrate concentration up to 10 000 mg L-1. Meanwhile, the obtained maximum voltage, current density, and power density were 322 mV, 1195 mA m-2, and 141.60 mW m-2, respectively, at the substrate concentration of 10 000 mg L-1. Present results suggested that the BEF system could be employed as an energy-saving and promising technology for antibiotic-containing wastewater treatment and simultaneous sustainable bioelectricity generation.

Determination of halogenated hydrocarbons in urine samples using a needle trap device packed with Ni/Zn-BTC bi-MMOF via the dynamic headspace method.

In this study, a nickel/zinc-BTC bi-metallic metal-organic framework (bi-MMOF) was employed as a new and efficient adsorbent in a needle trap device (NTD) for headspace (HS) sampling, extraction and analysis of halogenated hydrocarbons (trichloroethylene, tetrachloroethylene, chloroform, and tetrachloroethylene) from spiked and real urine samples. Characterization of the prepared adsorbent was accomplished by FT-IR, PXRD, EDX, elemental mapping, and FE-SEM techniques. According to experimental results, the optimal temperature and extraction time, salt content, temperature and desorption time of the response surface methodology (RSM) and Box-Behnken design (BBD) were determined to be 56 °C and 30 min, 5.5%, 350 °C and 8 min for the studied halogenated hydrocarbons, respectively. The calculated values of detection limit and quantitation limit parameters were in the range of 1.02-1.10 and 2.01-2.4.0 ng L-1, respectively. Moreover, intermediate precision and repeatability of the method were in the range of 4.90-8.20% and 1.50-4.80%, respectively. The recovery percentages of analytes were obtained to be in the range of 95.0-97.0% 10 days after the sampling and storage at 4 °C. This study showed that the proposed HS-NTD:Ni/Zn-BTC method coupled with a GC-FID can be employed as a simple, fast, and sensitive procedure for non-metabolized halogenated hydrocarbons from urine samples in biological monitoring.

Diuron degradation using three-dimensional electro-peroxone (3D/E-peroxone) process in the presence of TiO2/GAC: Application for real wastewater and optimization using RSM-CCD and ANN-GA approaches.

The present study investigates the efficiency of a three-dimensional electro-peroxone (3D/E-peroxone) reactor filled with TiO2-GAC in removing diuron from aqueous solution and in the remediation of real pesticide wastewater. The behavior of the system in terms of the effect of independent variables on diuron was investigated and optimized by RSM-CCD and ANN-GA methods. Both approaches proved to have a very good performance in the modeling of the process and determined the optimum condition of the independent variables as follows: initial pH = 10, applied current = 500 mA, supporting electrolyte = 0.07 M, ozone concentration = 10 mg L-1, and reaction time = 10 min. The 3D/E-peroxone process achieved a synergistic effect in diuron abatement and reduced significantly energy consumption, as compared to its individual components. H2O2 concentration generated in the electrolysis system was notably increased in the presence of TiO2-GAC microparticles. The BOD5/COD ratio of the real pesticide wastewater increased from 0.049 to 0.571 within 90 min treatment. Giving to the considerable enhancement of the biodegradability of the wastewater, this study strongly suggests that the 3D/E-peroxone process can be considered as a promising pretreatment step before a biological treatment process to produce intermediates which are more easily degradable by microorganisms.

A needle trap device packed with MIL-100(Fe) metal organic frameworks for efficient headspace sampling and analysis of urinary BTEXs.

The aim of this study was to develop a new method for the determination of benzene, toluene, ethylbenzene and xylene isomers (BTEXs) in urine samples. In this method, MIL-100(Fe)@Fe3 O4 @SiO2 metal-organic framework was synthesized, characterized and packed inside a needle trap device (NTD) as a sorbent for headspace extraction of unmetabolized BTEXs from urine samples followed by gas chromatography (GC) analysis. The GC device was equipped with a flame ionization detector (FID). The results showed that the optimal extraction time, extraction temperature and salt content were 60 min, 30°C and 5%, respectively. Also, the optimal desorption time and temperature were determined to be 1 min and 250°C, respectively. The limits of detection and quantification of the analytes of interest were in the ranges 0.0001-0.0005 and 0.0003-0.0014 µg ml-1 , respectively. The intra- and inter-day repeatability were <7.6%. The accuracy of the measurements in urine samples was in the range 7.1-11.4%. The results also demonstrated that the proposed NTD offered various advantages such as having high sensitivity and being inexpensive, reusable, user friendly, environmentally friendly and compatible for use with the GC device. Therefore, it can be efficiently used as a MIL-NTD for the extraction and analysis of unmetabolized BTEXs from urine samples.

Efficient extraction of aromatic amines in the air by the needle trap device packed with the zirconium based metal-organic framework sorbent.

In this study, development of a needle trap device (NTD) packed with UiO-66 adsorbent was used for the sampling of the aromatic amine compounds (including aniline, N,N-dimethylaniline and o-toluidine) followed by gas chromatography (GC) with flame-ionization detector (FID) analysis. The UiO-66 sorbent was synthesized and then packed inside a spinal needle (Gauge 22). The synthesized sorbent was characterized with the XRD, FE-SEM, EDS and FT-IR techniques. This study was conducted both in the laboratory and in the real samples. In the laboratory, the sampling parameters (such as temperature and humidity) and desorption parameters (including desorption temperature and desorption time) were optimized using Response Surface Methodology (RSM) by Central Composite Design (CCD). The results indicated that the performance of the sampling device decreased with increasing the sampling humidity and temperature. Moreover, the highest peak area responses of the studied analytes were observed at a desorption time of 3 minutes and desorption temperature of 270 °C. The values of the limit of detection (LOD) and limit of quantitation (LOQ) were in the range 0.01-0.02 and 0.03-0.05 ng mL-1, respectively. Our findings demonstrated that NTD packed with synthesized UiO-66 has good repeatability (RSD = 1.3-6.8%) and acceptable reproducibility (with three NTDs) (RSD = 1.3-9.7%). Comparison of the results between NTD-UiO-66 and NIOSH2002 showed a sufficient correlation (0.98-0.99) between two methods. Therefore, the results indicated that the NTD packed with the UiO-66 adsorbent can be used as a powerful technique for occupational and environmental monitoring.

Nano-hydroxyapatite/polyaniline composite as an efficient sorbent for sensitive determination of the polycyclic aromatic hydrocarbons in air by a needle trap device.

Hydroxyapatite is a readily available, inexpensive, environmentally friendly adsorbent with high adsorption capacity. In this study, a polyaniline-doped nano-hydroxyapatite (PANI@HA) adsorbent was synthesized and employed in a needle trap device for the extraction of polycyclic aromatic hydrocarbons such as naphthalene, fluoranthene, benzo[a]anthracene, phenanthrene, and benzo[a]pyrene for the first time. The synthesized adsorbent was characterized by X-ray diffraction, field emission scanning electron microscopy, and Fourier-transform infrared spectroscopy analysis. Initially, effective variables such as the carryover effect, storage time, accuracy, and precision of the method were examined in the laboratory. The desorption conditions were optimized using the response surface methodology and central composite design methods. From the standpoint of quantitative parameters, the limit of detection and limit of quantitation were determined to be between 0.001 and 0.003 and 0.021 and 0.051 ng mL-1, respectively, which indicates the high sensitivity of the proposed method. Additionally, no significant changes were detected after storage of analytes inside the needle at 4 °C after 60 days. The results of this study also provide a high correlation between the results of sampling with needles containing PANI@HA and with XAD-2 adsorbent tubes (standard NIOSH 5115 method) (R 2 = 0.98). Finally, the proposed method was successfully employed in the extraction and determination of polycyclic aromatic hydrocarbons in field (real) samples. In general, it can be concluded that a needle packed with PANI@HA is a reliable and high-performance method for sampling polycyclic aromatic hydrocarbons compared to the NIOSH method.

Development of a needle trap device packed with titanium-based metal-organic framework sorbent for extraction of phenolic derivatives in air.

We developed a novel method of needle trap device packed with titanium-based metal-organic framework for the extraction of phenolic derivatives in air followed by gas chromatography-flame ionization detector analysis. The synthetized adsorbent was packed inside a 22-gauge spinal needle. This method was first tested at laboratory scale, and then was used for field sampling of phenolic derivatives in air. A glass chamber placed on a heater at 60°C was used to provide different concentrations of phenolic derivatives. The desorption conditions and breakthrough volume were optimized using response surface methodology. The limit of detection and limit of quantitation of the proposed method were estimated to be in the range of 0.001-0.12 and 0.003-0.62 ng/mL, respectively, indicating a high sensitivity for the suggested sampler. Storing the packed needle trap device in a refrigerator at 4˚C for 60 days did not dramatically affect the storage stability. Our findings indicated that there was a high correlation coefficient (R2  = 0.99) between the measurement results of this method and the NIOSH recommended method (XAD-7 sorbent tube). Therefore, it can be concluded that the needle trap device packed with titanium-based metal-organic framework can be used as a efficient method for extraction of phenolic derivatives in air.